(2S,5S)-1,3-diaza-2-phospha-2-oxo-2-chloro-3-phenylbicyclo[3.3.0]octane | 110638-63-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,5S)-1,3-diaza-2-phospha-2-oxo-2-chloro-3-phenylbicyclo[3.3.0]octane
• 英文别名: (1S,3aS)-1-chloro-2-phenyl-3a,4,5,6-tetrahydro-3H-pyrrolo[1,2-c][1,3,2]diazaphosphole 1-oxide
• CAS: 110638-63-6
• 化学式: C₁₁H₁₄ClN₂OP
• 分子量: 256.672
• InChiKey: ZHVIQPOBBVJHCL-MEDUHNTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  23.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-(-)- α-甲基苄胺 、 (2S,5S)-1,3-diaza-2-phospha-2-oxo-2-chloro-3-phenylbicyclo[3.3.0]octane 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以80%的产率得到(5S)-1,3-diaza-2-[(S)-1-phenylethylamino]-2-phospha-2-oxo-3-phenylbicyclo[3.3.0]octane
  参考文献：
  名称：

  寻求含有NPO结构骨架的有效手性催化剂，用于硼烷介导的前手性酮的不对称还原

  摘要：

  含有N ＝ P ＝ O结构骨架的代表性手性催化剂，该骨架具有（5 S）-1，3-二氮杂-2-磷-2-氧代-3-苯基双环[3.3.0]辛烷部分，其氨基上具有不同的空间要求已经合成了磷，并描述了其在硼烷介导的前手性酮的不对称还原中的应用。

  DOI：

  10.1016/j.tetasy.2004.05.011
• 作为产物：
  描述：

  (S)-(+)-2-(苯胺甲基)吡咯烷 在 三乙胺 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以93%的产率得到(2R,5S)-1,3-diaza-2-phospha-2-oxo-2-chloro-3-phenylbicyclo(3.3.0)octane
  参考文献：
  名称：

  旋光性二氮杂环磷酰胺：新型有效试剂，可测定胺和醇的绝对构型

  摘要：

  各种胺和醇通过旋光性二氮杂环磷酰胺氯化物的作用转化为相应的磷酰胺，并且胺和醇的绝对构型可以通过形成的环磷酰胺的质子和磷NMR轻松确定。

  DOI：

  10.1039/c39950000435

文献信息

• A new chiral catalytic source with an N–PO structural framework containing a proximal hydroxyl group for the borane-mediated asymmetric reduction of prochiral ketones
  作者：Deevi Basavaiah、Gone Jayapal Reddy、Vanampally Chandrashekar

  DOI：10.1016/j.tetasy.2003.11.002

  日期：2004.1

  3S,5R)-2-Hydroxy-2,6,6-trimethylbicyclo[3.1.1]heptan-3-yloxy]-1,3-diaza-2-phospha-2-oxo-3-phenylbicyclo[3.3.0]octane has been successfully employed as a novel chiral catalytic source (4 mol %) for borane-mediated asymmetric reduction of prochiral ketones thus providing the resulting secondary alcohols with up to 96% enantiomeric excess.

  （5 S）-2-[（1 R，2 R，3 S，5 R）-2-羟基-2,6,6-三甲基双环[3.1.1]庚基-3-基氧基] -1,3-二氮杂-2-磷-2-氧代-3-苯基二环[3.3.0]辛烷已成功地用作新型手性催化源（4摩尔％），用于硼烷介导的前手性酮的不对称还原，从而使生成的仲醇具有较高的收率。对映体过量为96％。
• Optically active diazacyclophosphamides: novel efficient reagents for the determination of the absolute configuration of amines and alcohols
  作者：Tatsuo Oshikawa、Mitsuji Yamashita、Sadaaki Kumagai、Kuniaki Seo、Junichi Kobayashi

  DOI：10.1039/c39950000435

  日期：——

  Various amines and alcohols are converted into the corresponding phosphamides by the action of optically active diazacyclophosphamidic chlorides and absolute configurations of amines and alcohols are readily determined by proton and phosphorus NMR of the cyclophosphamides that are formed.

  各种胺和醇通过旋光性二氮杂环磷酰胺氯化物的作用转化为相应的磷酰胺，并且胺和醇的绝对构型可以通过形成的环磷酰胺的质子和磷NMR轻松确定。
• A novel and effective chiral phosphoramide catalyst for the borane-mediated asymmetric reduction of prochiral α-halo ketones
  作者：Deevi Basavaiah、Gone Jayapal Reddy、Vanampally Chandrashekar

  DOI：10.1016/s0957-4166(01)00101-x

  日期：2001.3

  The novel chiral phosphoramide, 1,4-bis[(5S)-1,3-diaza-2-phospha-2-oxo-3-phenylbicyclo(3.3.0)octan-2-yl]piperazine, was synthesised and successfully employed as a catalyst in the borane-mediated asymmetric reductions of prochiral cc-halo ketones, providing the corresponding a-halo alcohols in 90-95% enantiomeric purities. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Nonsimple relationships between the P∗-chiral diamidophosphite and the arylphosphine moieties in Pd-catalyzed asymmetric reactions: combinatorial approach and P,P∗-bidentate phosphine-diamidophosphites
  作者：Konstantin N. Gavrilov、Alexei A. Shiryaev、Sergey V. Zheglov、Vladislav K. Gavrilov、Nikolay N. Groshkin、Marina G. Maksimova、Alexandr N. Volov、Ilya A. Zamilatskov

  DOI：10.1016/j.tet.2013.12.006

  日期：2014.1

  A small family of P,P*-bidentate C-1-symmetric ligands containing 1,3,2-diazaphospholidine rings with stereogenic phosphorus atoms has been prepared. Palladium catalytic systems with these phosphine-diamidophosphites afforded 95% and 63% ees in asymmetric allylic substitution and desymmetrization processes, respectively. The influence of the nature of both the phosphine and diamidophosphite moieties of these compounds on the enantioselectivity is discussed. The 'mixed-ligand approach' in Pd-catalyzed asymmetric allylation with participation of some new P*-monodentate diamidophosphites and PPh3 is also considered. (C) 2013 Elsevier Ltd. All rights reserved.
• New chiral bicyclic phosphoramides derived from (L)-glutamic acid
  作者：Jean Francois Peyronel、Odile Samuel、Jean Claude Fiaud

  DOI：10.1021/jo00233a004

  日期：1987.11